Carbon radicals generated by solid polymers: Electron spin resonance spectroscopy for detection of species in water

Radicals generated in plastic medical devices (solid phase) by γ-rays or electron-beam irradiation during sterilization are known to cause oxidation of protein drugs, resulting in a loss or reduction in drug efficacy. The generation of radical species in water by the radical species in solid polymers has not been proved. Using electron spin resonance (ESR) spectroscopy, we confirm the generation of new radicals in water by γ-ray irradiated cyclic olefin polymers (COP). ESR measurements are obtained using 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPOL) as a spin probe and 5-(2,2-dimethyl-1,3-propoxycyclophosphoryl)-5-methyl-1-pyrroline N-oxide (CYPMPO) as a spin trap, in which the irradiated COP was immersed. The ESR signals indicate the TEMPOL radicals decline over time, suggesting the generation of new radicals. Conversely, the characteristic ESR signals of the adduct formed by the reaction between CYPMPO and the hydroxyl radical are observed. Thus, hydroxyl radicals are generated because of the migration of the radicals from COP to water. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48604.     

Molecular Features and Clinical Management of Hereditary Gynecological Cancers

Hereditary gynecological cancers are caused by several inherited genes. Tumors that arise in the female reproductive system, such as ovaries and the uterus, overlap with hereditary cancers. Several hereditary cancer-related genes are important because they might lead to therapeutic targets. Treatment of hereditary cancers should be updated in line with the advent of various new methods of evaluation. Next-generation sequencing has led to rapid, economical genetic analyses that have prompted a concomitant and significant paradigm shift with respect to hereditary cancers. Molecular tumor profiling is an epochal method for determining therapeutic targets. Clinical treatment strategies are now being designed based on biomarkers based on tumor profiling. Furthermore, the National Comprehensive Cancer Network (NCCN) guidelines significantly changed the genetic testing process in 2020 to initially consider multi-gene panel (MGP) evaluation. Here, we reviewed the molecular features and clinical management of hereditary gynecological malignancies, such as hereditary breast and ovarian cancer (HBOC), and Lynch, Li–Fraumeni, Cowden, and Peutz–Jeghers syndromes. We also reviewed cancer-susceptible genes revealed by MGP tests.     

Silver(I)-Ion-Mediated Cytosine-Containing Base Pairs: Metal Ion Specificity for Duplex Stabilization and Susceptibility toward DNA Polymerases

Spectroscopic characterization of Ag^I-ion-mediated C-Ag^I-A and C-Ag^I-T base pairs found in primer extension reactions catalyzed by DNA polymerases was conducted. UV melting experiments revealed that C-A and C-T mismatched base pairs in oligodeoxynucleotide duplexes are specifically stabilized by Ag^I ions in 1:1 stoichiometry in the same manner as a C-C mismatched base pair. Although the stability of the mismatched base pairs in the absence of Ag^I ions is in the order C-A≈C-T>C-C, the stabilizing effect of Ag^I ions follows the order C-C>C-A≈C-T. However, the comparative susceptibility of dNTPs to Ag^I-mediated enzymatic incorporation into the site opposite templating C is dATP>dTTP≫dCTP, as reported. The net charge, as well as the size and/or shape complementarity of the metal-mediated base pairs, or the stabilities of mismatched base pairs in the absence of metal ions, would be more important than the stability of the metallo-base pairs in the replicating reaction catalyzed by DNA polymerases.     

Design of a photocatalyst for bromate decomposition: surface modification of TiO2 by pseudo-boehmite

The rate of BrO3- reduction by a commercial TiO2 photocatalyst under UV illumination in an aqueous solution was increased by lowering the pH from 7 to 5. The effect is attributable to an enhancement of the electrical interaction between BrO3- and the positively charged surfaces of the TiO2 photocatalyst. The surface charge can be controlled by a surface modification of the TiO2 photocatalyst without controlling the pH of the water. In fact, the isoelectric point of surface-modified TiO2 was higher than that of the unloaded TiO2 photocatalyst, resulting in an increase in the rate of the photocatalytic reduction of BrO3- at a neutral pH. This increase is explained by an increase in the amount of adsorbed BrO3- on the photocatalyst surface.     

Carbon Nitride Loaded with an Ultrafine,Monodisperse, Metallic Platinum-Cluster Cocatalyst for the Photocatalytic Hydrogen-Evolution Reaction

For the realization of a next-generation energy society, further improvement in the activity of water-splitting photocatalysts is essential. Platinum (Pt) is predicted to be the most effective cocatalyst for hydrogen evolution from water. However, when the number of active sites is increased by decreasing the particle size, the Pt cocatalyst is easily oxidized and thereby loses its activity. In this study, a method to load ultrafine, monodisperse, metallic Pt nanoclusters (NCs) on graphitic carbon nitride is developed, which is a promising visible-light-driven photocatalyst. In this photocatalyst, a part of the surface of the Pt NCs is protected by sulfur atoms, preventing oxidation. Consequently, the hydrogen-evolution activity per loading weight of Pt cocatalyst is significantly improved, 53 times, compared with that of a Pt-cocatalyst loaded photocatalyst by the conventional method. The developed method is also effective to enhance the overall water-splitting activity of other advanced photocatalysts such as SrTiO₃ and BaLa₄Ti₄O₁₅.     

Sequestration of muscarinic acetylcholine receptor m2 subtypes. Facilitation by G protein-coupled receptor kinase (GRK2) and attenuation by a dominant-negative mutant of GRK2

Sequestration of m2 receptors (muscarinic acetylcholine receptor m2 subtypes), which was assessed as loss of N-[3H]methylscopolamine ([3H]NMS) binding activity from the cell surface, was examined in COS 7 and BHK-21 cells that had been transfected with expression vectors encoding the m2 receptor and, independently, vectors encoding a G protein-coupled receptor kinase (GRK2) (beta-adrenergic receptor kinase 1) or a GRK2 dominant-negative mutant (DN-GRK2). The sequestration of m2 receptors became apparent when the cells were treated with 10(-5) M or higher concentrations of carbamylcholine. In this case, approximately 40% or 20-25% of the [3H]NMS binding sites on COS 7 or BHK-21 cells, respectively, were sequestered with a half-life of 15-25 min. In cells in which GRK2 was also expressed, the sequestration became apparent in the presence of 10(-7) M carbamylcholine. Approximately 40% of the [3H]NMS binding sites on both COS 7 and BHK-21 cells were sequestered in the presence of 10(-6) M or higher concentrations of carbamylcholine. When DN-GRK2 was expressed in COS 7 cells, the proportion of [3H]NMS binding sites sequestered in the presence of 10(-5) M or higher concentrations of carbamylcholine was reduced to 20-30%. These results indicate that the phosphorylation of m2 receptors by GRK2 facilitates their sequestration. These results are in contrast with the absence of a correlation between sequestration and the phosphorylation of beta-adrenergic receptors by the GRK2 and suggests that the consequences of phosphorylation by GRK2 are different for different receptors.     

High temperature superconductor micro-superconducting-quantum-interference-device magnetometer for magnetization measurement of a microscale magnet

We have developed a high temperature superconductor (HTS) micrometer-sized dc superconducting quantum interference device (SQUID) magnetometer for high field and high temperature operation. It was fabricated from YBa2Cu3O7-delta of 92 nm in thickness with photolithography techniques to have a hole of 4x9 microm2 and 2 microm wide grain boundary Josephson junctions. Combined with a three dimensional magnetic field coil system, the modulation patterns of critical current Ic were observed for three different field directions. They were successfully used to measure the magnetic properties of a molecular ferrimagnetic microcrystal (23x17x13 microm3), [Mn2(H2O)2(CH3COO)][W(CN)8]2H2O. The magnetization curve was obtained in magnetic field up to 0.12 T between 30 and 70 K. This is the first to measure the anisotropy of hysteresis curve in the field above 0.1 T with an accuracy of 10(-12) J T(-1) (10(-9) emu) with a HTS micro-SQUID magnetometer.     

Mixed Lubrication with C18 Fatty Acids: Effect of Unsaturation

In this paper, the lubrication mechanism of fatty acids is revisited with a new approach combining experimental and computational chemistry studies. The lubricating properties of single and mixtures of stearic, oleic and linoleic acids in a synthetic Poly-Alpha-Olefin base oil (PAO4) on iron oxide surface are investigated under mixed boundary regime with temperatures from 50 °C up to 150 °C. Low friction coefficient (about 0.055) with no visible wear is reported in the presence of single stearic acid at high temperature. This lubricating behavior is inhibited in the presence of unsaturated fatty acids highlighting an anti-synergic effect of a saturated/unsaturated mixture, especially at 150 °C. To understand the anti-synergic effect and the adsorption mechanism of these molecules, molecular dynamic (MD) and quantum chemistry simulations are performed to evaluate their diffusion coefficient in PAO4 and their adsorption mechanism on iron oxide at different temperatures. MD simulation results show a faster diffusion toward the surface for unsaturated fatty acids than for saturated fatty acid at all the studied temperatures. This means that unsaturated molecules arrive and mainly adsorb before stearic acid on the surface leading to a tribological behavior of the mixture characteristic of the unsaturated molecule. Computational chemistry suggests that all fatty acids (saturated and unsaturated) adsorption mechanism is due to the chemisorption of the carboxylic group on iron oxide surface with no desorption up to 150 °C.